Resin-rubber composite

Abstract

To provide a resin-rubber composite having a resin as a base material, which has improved not only an initial adhesion property but also durable adhesion properties such as alkali resistance and warm water resistance.SOLUTION: A resin-rubber composite is formed by stacking, (1a) an organic metallic compound having a chelate ring represented by the general formula (M1: titanium, zirconium, or tin, R: an alkyl group having carbon numbers 1-8, R': a methyl group or an OR group, n: an integer of 1-3), and an alkoxyl group, or (1b) a mixture of the organic metallic compound, and (2) a surface treatment agent layer containing silica in a weight ratio of 90:10 to 50:50 as a solid content ratio, and does not contain a silane coupling agent or its oligomers, a silane-based adhesive layer being an overcoat layer, and an EPDM layer being a rubber layer, or a phenol resin-based adhesive layer being an overcoat layer, a fluorine rubber layer being a rubber layer, and a nitrile rubber layer or a hydrogenated nitrile rubber layer, in this order on an adhesion surface with a rubber of a resin molded article.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin-rubber composite, and more particularly to a resin-rubber composite having excellent durable adhesion. [Background technology]

[0002] Metals such as brass and stainless steel are used as materials for diaphragms and valves due to their durability, including water resistance and alkali resistance, but resins such as polyphenylene sulfide resin (PPS), polytetrafluoroethylene resin (PTFE), and polyacetal resin (POM) are also used to make the parts lighter.

[0003] These substrates are poorly adhesive to rubber, and it is difficult to ensure stable adhesion between them. Therefore, a method is used in which the substrate is subjected to a surface treatment and then coated with an adhesive containing a synthetic resin, a chlorinated rubber resin, a metal oxide, a silane coupling agent, or the like.

[0004] Surface roughening is a common surface treatment, but surface roughening can cause breakage and deformation, especially in the case of PPS resin. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 4,953,564 Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a resin-rubber composite having a lightweight resin as a base material, which has improved not only initial adhesion but also durable adhesion properties such as alkali resistance and warm water resistance. [Means for solving the problem]

[0007] The object of the present invention is to provide a resin molded product having a surface bonded to rubber, (1a) General formula TIFF2025128510000001.tif35154 (wherein M1 is titanium, zirconium, or tin, R is an alkyl group having 1 to 8 carbon atoms, R' is a methyl group or an OR group, and n is an integer of 1 to 3) or a compound of the general formula an organometallic compound having at least one chelate ring and an alkoxyl group, represented by TIFF2025128510000002.tif35154 (wherein M2 is aluminum, R is an alkyl group having 1 to 8 carbon atoms, R' is a methyl group or an OR group, and m is 1 or 2), or (1b) a mixture of the organometallic compound and a metal alkoxide compound, and (2) silica, in a weight ratio of 90:10 to 50:50 as a solid content ratio, and comprising a surface treatment agent that does not contain a silane coupling agent or an oligomer thereof. and This is achieved by a resin-rubber composite formed by sequentially laminating a silane-based adhesive layer as a top coat layer and an EPDM rubber layer, or a phenolic resin-based adhesive layer as a top coat layer and a fluororubber layer, a nitrile rubber layer or a hydrogenated nitrile rubber layer. [Effects of the Invention]

[0008] The resin-rubber composite of the present invention is lighter than a metal-rubber composite, and exhibits the effects of not only excellent initial adhesion but also excellent durable adhesion such as alkali resistance and warm water resistance, without the need for roughening the resin surface. DETAILED DESCRIPTION OF THE INVENTION

[0009] Resins that can be used include polyphenylene sulfide (PPS) resin, polytetrafluoroethylene (PTFE) resin that has been defluorinated by plasma treatment or metallic sodium treatment, polyacetal (POM) resin, polyimide (PI) resin, polyethylene (PE) resin, polyethylene terephthalate (PET) resin, polypropylene (PP) resin, etc., and preferably PPS resin or PTFE resin that has been defluorinated by plasma treatment or metallic sodium treatment, etc. A primer layer is formed on the bonding surface of these resin molded products with rubber using a surface treatment agent.

[0010] As the surface treatment agent, among the surface treatment agents previously proposed by the applicant in Patent Document 1, the surface treatment agent represented by the general formula (1a) TIFF2025128510000003.tif35154 (wherein M1 is titanium, zirconium, or tin, R is an alkyl group having 1 to 8 carbon atoms, R' is a methyl group or an OR group, and n is an integer of 1 to 3) or a compound of the general formula The composition contains an organometallic compound having at least one chelate ring and an alkoxyl group, represented by the formula TIFF2025128510000004.tif35154 (wherein M2 is aluminum, R is an alkyl group having 1 to 8 carbon atoms, R' is a methyl group or an OR group, and m is 1 or 2), or (1b) a mixture of the organometallic compound and a metal alkoxide compound, and (2) silica, in a weight ratio of 90:10 to 50:50 as a solid content, and does not contain a silane coupling agent or its oligomer.

[0011] general formula TIFF2025128510000005.tif35154R:CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, i-C4H9, i-C8H 17 etc. Alkyl groups with 1 to 8 carbon atoms R': CH3 group or OR M1: Ti, Zr, Sn n: an integer between 1 and 3 Examples of the organometallic compound represented by the formula (I) include diisopropoxytitanium bis(methylacetoacetate), diisopropoxytitanium bis(ethylacetoacetate), diisopropoxytitanium bis(propylacetoacetate), diisopropoxytitanium bis(butylacetoacetate), diisopropoxytitanium bis(hexylacetoacetate), di-n-propoxytitanium bis(methylacetoacetate), di-n-propoxytitanium bis(ethylacetoacetate), di-n- Propoxytitanium bis(propyl acetoacetate), di-n-propoxytitanium bis(butyl acetoacetate), di-n-propoxytitanium bis(hexyl acetoacetate), di-n-butoxytitanium bis(methyl acetoacetate), di-n-butoxytitanium bis(ethyl acetoacetate), di-n-butoxytitanium bis(propyl acetoacetate), di-n-butoxytitanium bis(butyl acetoacetate), di-n-butoxytitanium bis(hexyl acetoacetate), 1,Organic titanium compounds such as 3-propanedioxytitanium bis(ethyl acetoacetate), diisopropoxytitanium bis(acetylacetonate), di-n-propoxytitanium bis(acetylacetonate), di-n-butoxytitanium bis(acetylacetonate), titanium tetraacetylacetonate, titanium tetraethyl acetoacetate, titanium tetrapropyl acetoacetate, and titanium tetrabutyl acetoacetate; diisopropoxyzirconium bis(methyl acetoacetate), diisopropoxyzirconium bis(ethyl acetoacetate), diisopropoxyzirconium bis(propyl acetoacetate), diisopropoxyzirconium bis(butyl acetoacetate), and diisopropoxyzirconium bis(methyl acetoacetate). di-n-propoxyzirconium bis(hexylacetoacetate), di-n-propoxyzirconium bis(methylacetoacetate), di-n-propoxyzirconium bis(ethylacetoacetate), di-n-propoxyzirconium bis(propylacetoacetate), di-n-propoxyzirconium bis(butylacetoacetate), di-n-propoxyzirconium bis(hexylacetoacetate), di-n-butoxyzirconium bis(methylacetoacetate), di-n-butoxyzirconium bis(ethylacetoacetate), di-n-butoxyzirconium bis(propylacetoacetate), di-n-butoxyzirconium bis(butylacetoacetate), di-n-butoxyzirconium bis(hexylacetoacetate), 1,Organic zirconium compounds such as 3-propanedioxyzirconium bis(ethyl acetoacetate), diisopropoxyzirconium bis(acetylacetonate), di-n-propoxyzirconium bis(acetylacetonate), di-n-butoxyzirconium bis(acetylacetonate), diisopropoxytin bis(methyl acetoacetate), diisopropoxytin bis(ethyl acetoacetate), diisopropoxytin bis(propyl acetoacetate), diisopropoxytin bis(butyl acetoacetate), diisopropoxytin bis(hexyl acetoacetate), di-n-propoxytin bis(methyl acetoacetate), di-n-propoxytin bis(ethyl ... tin compounds such as di-n-butoxytin bis(propyl acetoacetate), di-n-propoxytin bis(butyl acetoacetate), di-n-propoxytin bis(hexyl acetoacetate), di-n-butoxytin bis(methyl acetoacetate), di-n-butoxytin bis(ethyl acetoacetate), di-n-butoxytin bis(propyl acetoacetate), di-n-butoxytin bis(butyl acetoacetate), di-n-butoxytin bis(hexyl acetoacetate), 1,3-propanedioxytin bis(ethyl acetoacetate), diisopropoxytin bis(acetylacetonate), di-n-propoxytin bis(acetylacetonate), and di-n-butoxytin bis(acetylacetonate), and also compounds represented by the general formula: TIFF2025128510000006.tif35154R:CH3, C2H5, n-C3H7, i-C3H7, n-C4H9, i-C4H9, i-C8H 17 etc. Alkyl groups with 1 to 8 carbon atoms R': CH3 group or OR M2:Al m:1 or 2 Examples of the organometallic compound represented by the formula (I) include diisopropoxyaluminum mono(methyl acetoacetate), diisopropoxyaluminum mono(ethyl acetoacetate), diisopropoxyaluminum mono(propyl acetoacetate), diisopropoxyaluminum mono(butyl acetoacetate), diisopropoxyaluminum mono(hexyl acetoacetate), di-n-propoxyaluminum mono(methyl acetoacetate), di-n-propoxyaluminum mono(ethyl acetoacetate), di-n-propoxyaluminum mono(propyl acetoacetate), dibutoxyaluminum mono(butyl acetoacetate), di-n-propoxyaluminum mono(hexyl acetoacetate), dibutoxyaluminum mono(methyl acetoacetate), dibutoxyaluminum mono(ethyl acetoacetate), dibutoxyaluminum mono(propyl acetoacetate), dibutoxyaluminum mono(butyl acetoacetate), dibutoxyaluminum mono(hexyl acetoacetate), diisopropoxyaluminum mono(acetyl acetonate), etc. Furthermore, these organometallic compounds having at least one chelate ring and an alkoxyl group can also be used as a mixture with a metal alkoxide compound, and examples of the metal alkoxide compound include tetra-i-propoxytitanium, tetra-n-propoxytitanium, tetra-n-butoxytitanium, tetra(2-ethylhexyl)titanate, tetra-i-propoxyzirconium, tetra-n-propoxyzirconium, tetra-n-butoxyzirconium, tetra-i-propoxytin, tetra-n-propoxytin, tetra-n-butoxytin, triisopropoxyaluminum, mono-sec-butoxydipropoxyaluminum, tri-sec-butoxyaluminum, tri(2-ethylhexyl)aluminum, etc. Among the organometallic compounds, organotitanium compounds are preferably used, and organometallic compounds can be used as a mixture of one or more types.

[0012] The silica (silicon oxide) used is a dispersion of dry or wet silica with an SiO2 content of 85% or more in an organic solvent or water, preferably so-called colloidal silica, which is a colloidal dispersion of high-purity anhydrous silica particles in an organic solvent or water. The colloidal silica has an average particle size of 1 to 50 nm, preferably 10 to 30 nm, and is dispersed in an organic solvent such as methanol, methyl ethyl ketone, or methyl isobutyl ketone. Examples of commercially available products include Methanol Silica Sol (a Nissan Chemical Industries product; dispersed in methanol at a solids concentration of 30% by weight), Snowtex MEK-ST (a Nissan Chemical Industries product; dispersed in methyl ethyl ketone at a solids concentration of 30% by weight), and Snowtex MIBK-ST (a Nissan Chemical Industries product; dispersed in methyl isobutyl ketone at a solids concentration of 30% by weight).

[0013] The organometallic compound and silica are used in a weight ratio of 90:10 to 50:50 in terms of solid content, preferably 70:30 to 50:50. Here, the solid content of the organometallic compound refers to the amount of residue remaining after evaporating the compound to dryness at 135°C for one hour. This amount is an indicator of the amount of organometallic compound remaining on the substrate when actually used for surface treatment. The organic solvent solution is prepared so that the total solid content is approximately 0.01 to 5 wt%. If the silica content is higher than this, the heat resistance decreases, resulting in peeling after high-temperature heating. On the other hand, if the silica content is lower than this, the liquid resistance durability against water, LLC, etc. deteriorates. Examples of organic solvents that can be used include alcohols such as methanol, ethanol, and isopropanol; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; and polyhydric alcohols such as ethylene glycol monomethyl ether, monoethyl ether, monobutyl ether, and monoethyl ether acetate, or derivatives thereof.

[0014] In addition, when a surface treatment agent consisting of a silane coupling agent or its oligomer, an organometallic compound and silica is used, for example, by adding an equal weight of the silane coupling agent oligomer to the organometallic compound, the water resistance and heat resistance are significantly reduced, making it difficult to achieve the object of the present invention, and the storage stability of the surface treatment agent formulation is also extremely poor. For this reason, even if such prior art existed before the present application, it should be distinguished in the present invention from them.

[0015] As a surface treatment agent containing the above components as essential components, a commercially available product, for example, J50F manufactured by NOK, can be used as is. Such a surface treatment agent can be applied to the adhesive surface of the resin molded product with rubber at a concentration of 10 to 1000 mg / m by immersion, spraying, brushing, roll coating, or other methods. 2 , preferably 50 to 500 mg / m 2 After drying at room temperature or with hot air, it is baked at 80 to 250°C for 0.5 to 30 minutes to form a primer layer.

[0016] After the undercoat layer is applied to the resin molded product and dried, a topcoat layer is formed using an adhesive appropriate for the type of rubber to be bonded. Examples of rubber include fluororubber, EPDM rubber, nitrile rubber (NBR), and hydrogenated nitrile rubber (HNBR), and the adhesive used for EPDM is a silane-based adhesive, while for NBR and HNBR, a phenolic resin-based adhesive is used.

[0017] The silane-based adhesive is a hydrolysis condensation product of organoalkoxysilane, which is represented by the general formula R ′ Si(OR)3, where R is a lower alkyl group such as a methyl group or an ethyl group, and R ′ is a methyl group, an ethyl group, a 3-aminopropyl group, an N-(2-aminoethyl)-3-aminopropyl group, an N-phenyl-3-aminopropyl group, a vinyl group, a 3-methacryloxypropyl group, a 3-glycidoxypropyl group, a 3-mercaptopropyl group, and the like.

[0018] The hydrolysis and condensation reaction of organoalkoxysilanes is carried out by heating to approximately 40 to 80°C in the presence of water for hydrolysis and an acid catalyst such as formic acid. Furthermore, as such hydrolysis and condensation products, copolymerized oligomers of amino group-containing alkoxysilanes and vinyl group-containing alkoxysilanes are preferably used. Examples of the amino group-containing alkoxysilane, which is one component of the copolymerized oligomer, include γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, and N-β-(aminoethyl)-γ-aminopropyltriethoxysilane. Examples of the vinyl group-containing alkoxysilane, which is the other component, include vinyltrimethoxysilane and vinyltriethoxysilane.

[0019] In the oligomerization reaction, 25 to 400 parts by weight, preferably 50 to 150 parts by weight, of vinyl-containing alkoxysilane and 20 to 150 parts by weight of water for hydrolysis are used per 100 parts by weight of amino-containing alkoxysilane. If a larger proportion of vinyl-containing alkoxysilane is used, compatibility with the topcoat or rubber deteriorates, resulting in reduced adhesion. On the other hand, if a smaller proportion is used, water resistance deteriorates.

[0020] The oligomerization reaction involves placing these components in a reactor equipped with a distillation apparatus and a stirrer and stirring at approximately 60°C for approximately 1 hour. Then, approximately 1 to 2 moles of acid, such as formic acid or acetic acid, are added per mole of amino-containing alkoxysilane within 1 hour. The temperature is maintained at approximately 65°C. The reaction is continued for an additional 1 to 5 hours with stirring, while the alcohol produced by hydrolysis is distilled under reduced pressure. The distillation is terminated when only water remains in the distillate. The desired copolymerized oligomer is then obtained by diluting the distillate to a silane concentration of 30 to 80% by weight. This copolymerized oligomer is soluble in alcoholic organic solvents such as methanol and ethanol. Alternatively, commercially available copolymerized oligomers can be used as is.

[0021] It is preferable to further add an organometallic compound to these silane adhesives. Examples of the organometallic compound include organoaluminum compounds such as triisopropoxyaluminum, mono-sec-butoxydipropoxyaluminum, tri-sec-butoxyaluminum, ethyl acetoacetate aluminum diisopropylate, aluminum tris(ethyl acetoacetate), aluminum monoacetylacetonate bis(ethyl acetoacetate), and aluminum tris(acetylacetate); tetraisopropoxytitanium, tetra-n-butoxytitanium, isopropoxytitanium bis(ethyl acetoacetate), and 1 Examples include organic titanium compounds such as 3-propanedioxytitanium bis(ethylacetoacetate), diisopropoxytitanium bis(acetylacetonate), and titanium tetraacetylacetonate; organic zirconium compounds such as tetra-n-propylzirconium, tetra-n-butoxyzirconium, di-n-butoxyzirconium bis(acetylacetonate), and di-n-butoxyzirconium bis(ethylacetoacetate); and organic tin compounds such as dibutyltin dilaurate, dibutyltin dioctate, and dibutyltin dilaurate.

[0022] These organometallic compounds are used in a proportion of about 100 parts by weight or less, preferably about 20 to 80 parts by weight, per 100 parts by weight of the hydrolysis-condensation product. Addition of the organometallic compound in such a proportion increases liquid resistance to heated water, ethylene glycol or its aqueous solution, alcohol, etc. On the other hand, if used in a proportion greater than this, compatibility with rubber deteriorates, resulting in reduced adhesion.

[0023] Silane-based adhesives, which contain the above components as essential ingredients, are generally prepared and used as solutions with a concentration of approximately 0.2 to 3% by weight in a mixed solvent of water and an alcohol-based organic solvent such as methanol, ethanol, or isopropanol, or a ketone-based organic solvent such as acetone or methyl ethyl ketone. The organic solvent and water are mixed in a ratio of approximately 100 to 80% by weight of the former and approximately 0 to 20% by weight of the latter. When water is used in combination, the hydrolysis condensation product further increases in molecular weight, allowing the formation of a tough coating.

[0024] In addition, commercially available silane adhesives such as Chemlok AP-133 manufactured by Lord Japan Inc., Metalok S-2 manufactured by Toyo Kagaku Kenkyusho, and Megam 3290-1 manufactured by Rohm and Haas can also be used after diluting them with an alcohol-based solvent or an alcohol-water mixed solvent.

[0025] As the phenolic resin adhesive, commercially available products such as Metalock N31 (Toyo Kagaku Kenkyusho), Sixon 715 (DDP Specialty Products Japan), TS1677-13 (Lord Japan Inc.), and Chemlock 205 (Lord Japan Inc.) can generally be used as is, with a blend of novolac phenolic resin and resol phenolic resin in a ratio of 9:1 to 1:9 being preferred. The adhesive is applied by dipping or spraying, dried at room temperature or with warm air, and then baked at 80 to 250°C for 1 to 30 minutes to form a topcoat layer.

[0026] An intermediate coat layer is preferably provided between the primer coat and the top coat. Such intermediate coat layers can be vulcanizing adhesives containing phenolic resin and epoxy resin, typically commercially available products such as Metalock PH-37 (Toyo Kagaku Kenkyusho) or Chemlok XPJ-60 (Lord Japan Inc.). These intermediate coat adhesives are typically prepared as organic solvent solutions containing alcoholic organic solvents such as methanol, ethanol, or isopropanol, or ketone organic solvents such as acetone, methyl ethyl ketone, or methyl isobutyl ketone, either alone or in combination, at a concentration of approximately 0.1 to 20% by weight. These solutions are applied using the same application method as for surface treatment agents, dried at room temperature or with warm air, and then baked at 80 to 250°C for 1 to 30 minutes to form the intermediate coat layer. The application of such an intermediate coat layer further improves LLC resistance at temperatures between 85 and 120°C.

[0027] Onto the topcoat layer thus formed, an unvulcanized fluororubber compound, EPDM compound, nitrile rubber compound, or hydrogenated nitrile rubber compound is applied as an organic solvent solution, dried at room temperature to about 100°C for about 1 to 15 minutes, and the organic solvent (e.g., alcohols such as methanol or ethanol, ketones such as methyl ethyl ketone or methyl isobutyl ketone, aromatic hydrocarbons such as toluene or xylene, or mixed solvents thereof) is evaporated. Then, pressure crosslinking is carried out at 150 to 250°C for 30 seconds to 10 minutes, followed by secondary crosslinking at 100 to 250°C for 1 to 24 hours, forming a rubber layer and producing a rubber-resin laminate. The composition of these rubber compounds is not particularly limited, but examples of the composition are as follows: (Combination example I) EPDM (Mitsui Chemicals EPT1070H) 100 parts by weight FEF Carbon Black 30% Titanium dioxide 70% Stearic acid 1.3 〃 Anti-aging agent (Ouchi Shinko Chemical Products Nocrac White) 2 Same Polyterpene resin (Goodyear Wingtack 95) 5 Dicumyl peroxide (Nippon Oil Products Percumyl D) 5 〃 Triallyl cyanurate (Degussa Activator OC) 3 (Combination example II) Fluorine rubber (DuPont Viton GLT305) 100 parts by weight SRF Carbon Black 25 〃 Sodium stearate 1 〃 Triallyl isocyanurate (Nippon Kasei TAIC) 3 Same Organic peroxide (Nippon Oil Products Perhexa 25B-40) 3 Same as above (Combination example III) NBR (Japan Synthetic Rubber Products N237: Medium-High Nitrile) 100 parts by weight HAF carbon black 10 〃 SRF Carbon Black 40 〃 Powdered cellulose 10 〃 Zinc oxide 10% Stearic acid 1 〃 Microcrystalline wax 2 〃 Anti-aging agent (Ouchi Shinko Chemical Products ODA-NS) 4 Same Plasticizer (Bayer's Bucanol OT) 5 Organic peroxide (Nippon Oil Products Perhexa 25B) 6 Same N,Nm-phenylenedimaleimide 1 〃 (Combination example IV) Hydrogenated NBR (Zetpol 2020, a product of Nippon Zeon) 100 parts by weight SRF Carbon Black 60% Graphite 10 Powdered cellulose 10 〃 Stearic acid 1 〃 Anti-aging agent (Ouchi Shinko Chemical Products Nocrac CD) 1 Same Anti-aging agent (Ouchi Shinko Chemical Products Nocrac MMB) 0.4 Same as above Microcrystalline wax 1 〃 Plasticizer (Asahi Denka RS-735) 15 〃 Organic peroxide (Nippon Oil Products Peroximon F40) 7.5 〃 N,Nm-phenylenedimaleimide 2 [Example]

[0028] The present invention will now be described in detail with reference to examples, although the present invention, including its effects, is not limited to these examples.

[0029] Example 1 A surface treatment agent (NOK product J50F; solids ratio of organometallic compound to silica 60:40) was applied by dip coating to the adhesive surface of polyphenylene sulfide resin (DIC product A504X90) with rubber. After drying at room temperature, the resin was baked at 200°C for 10 minutes to form a surface treatment layer.

[0030] A 0.02 to 2.0 wt% methanol diluted solution of a silane adhesive (Chemlock AP-133, a product of Lord Japan Inc.) was applied onto the surface treatment layer by dip coating, dried at room temperature, and then baked at 150°C for 5 minutes to form a topcoat layer.

[0031] An uncrosslinked EPDM rubber compound (Compound Example I) was bonded onto the topcoat layer, and pressure crosslinking was carried out at 180°C for 6 minutes, followed by secondary crosslinking at 150°C for 1 hour to obtain a rubber laminate.

[0032] Example 2 In Example 1, a methyl ethyl ketone diluted solution of phenolic resin and epoxy resin adhesive (Metalock PH-37, a product of Toyo Kagaku Kenkyusho) serving as an intermediate coating agent was applied onto the surface treatment layer by dip coating, dried at room temperature, and then baked at 200°C for 10 minutes to form an intermediate coating layer between the surface treatment layer and the topcoat layer.

[0033] Example 3 In Example 1, polytetrafluoroethylene resin (Nichias product 9000-G25) that had been defluorinated by metallic sodium treatment was used instead of polyphenylene sulfide resin.

[0034] Example 4 In Example 2, polytetrafluoroethylene resin (9000-G25) was used instead of polyphenylene sulfide resin.

[0035] Example 5 In Example 2, the fluororubber compound of Compounding Example II was used in place of the EPDM rubber compound.

[0036] Example 6 In Example 2, a phenolic resin adhesive (Dow Chemical product Thixon 715) was used instead of the silane adhesive, and the NBR rubber compound of Formulation Example III was used instead of the EPDM rubber compound.

[0037] Example 7 In Example 2, a phenolic resin adhesive (Thixon 715) was used in place of the silane adhesive, and the hydrogenated NBR rubber compound of Compounding Example IV was used in place of the EPDM rubber compound.

[0038] Comparative Example 1 In Example 1, no surface treatment layer was formed.

[0039] Comparative Example 2 In Example 1, no topcoat layer was applied.

[0040] Comparative Example 3 In Example 1, a silane-based adhesive (AP-133) was used to form the surface treatment layer.

[0041] Comparative Example 4 In Example 2, no surface treatment was performed.

[0042] Comparative Example 5 In Example 1, an alkylsilane coupling agent (Dow Toray product OFS-6366) was used instead of the silane adhesive.

[0043] Comparative Example 6 In Example 2, an alkylsilane coupling agent (OFS-6366) was used instead of the silane adhesive.

[0044] The resin-rubber composites obtained in the above examples and comparative examples were used to evaluate adhesiveness. Adhesion: JIS K6256-2 "90° peel strength with hard plate" and physical test using pliers By destructive test, initial, 85℃ hot water or 85℃, 105℃ or 120℃ In all cases, the R retention rate (%) was measured after immersion for 72 hours, 240 hours, and 720 hours. The following was evaluated: 95-100% is ◎, 90-94% is ○, 50-89% is △, 0-49% is ×

[0045] The results obtained are shown in the following table: In Comparative Example 2, the adhesion to the rubber was insufficient at the initial stage, causing peeling, and further testing could not be carried out. table Example Comparative Example 1 2 3 4 5 6 7 1 2 3 4 5 6 Initial ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ ◎ × ◎ ◎ ○ ○ After soaking in 85℃ warm water for 72 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ - ○ ○ △ △ After soaking in 85℃ warm water for 240 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ - ○ ○ △ △ After soaking in 85℃ warm water for 720 hours ◎ ◎ ◎ ◎ ◎ ◎ ◎ ○ - ○ ○ △ △ 85℃LLC, after 72 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 85℃LLC, after 240 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 85℃LLC, after 720 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 105℃LLC, after 72 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 105℃LLC, after 240 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 105℃LLC, after 720 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 120℃LLC, after 72 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 120℃LLC, after 240 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ 120℃LLC, after 720 hours immersion ○ ◎ ○ ◎ ◎ ◎ ◎ × - × △ △ △ [Industrial Applicability]

[0046] The resin-rubber composite of the present invention exhibits excellent resistance to (hot) water and chemicals, and is therefore effectively used as a material for diaphragms and valves.

Claims

1. On the adhesive surface between the rubber and resin molded products, (1a) General formula (where M 1 is titanium, zirconium or tin, R is an alkyl group having 1 to 8 carbon atoms, R' is a methyl group or an OR group, and n is an integer of 1 to 3), or a group represented by the general formula (where M 2 an organometallic compound having at least one chelate ring and an alkoxyl group represented by the formula (1a), (1b) wherein R is aluminum, R is an alkyl group having 1 to 8 carbon atoms, R' is a methyl group or an OR group, and m is 1 or 2, or a mixture of the organometallic compound and a metal alkoxide compound, and (2) silica, in a weight ratio of 90:10 to 50:50 as a solid content ratio, and comprising a surface treatment agent that does not contain a silane coupling agent or an oligomer thereof. and A resin-rubber composite obtained by sequentially laminating a silane-based adhesive layer as a top coat layer and an EPDM rubber layer, or a phenolic resin-based adhesive layer as a top coat layer and a fluororubber layer, a nitrile rubber layer, or a hydrogenated nitrile rubber layer.

2. 2. The resin-rubber composite according to claim 1, further comprising a vulcanized adhesive layer containing a phenolic resin and an epoxy resin provided between the surface treatment layer and the top coat layer.

3. 3. The resin-rubber composite according to claim 1, wherein the resin is a polyphenylene sulfide resin, a polytetrafluoroethylene resin, or a polyacetal resin.

4. 3. The resin-rubber composite according to claim 1, wherein the silane-based adhesive is an adhesive comprising a copolymer oligomer of an amino-group-containing alkoxysilane and a vinyl-group-containing alkoxysilane.

5. 3. The resin-rubber composite according to claim 1, wherein the phenolic resin adhesive is an adhesive in which novolak phenolic resin and resol phenolic resin are blended in a ratio of 9:1 to 1:

9.

6. 3. The resin-rubber composite according to claim 1, which is a valve or a diaphragm.

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